Crystalline form of a bis-triazinylamino stilbene optical brightener and process for making same



p 7 3,472,842 C6 Patented Oct. 14, 1969 United States Patent desirable discoloration often increases when these pow- 3.,472,842 ders are stored in a damp atmosphere. The freedom from CRYSTALLINE FORM OFABI -TRQ ZIN discoloration of the Washing powder itself during the STILBENE OP I BRIGHTENILR AND PROC' several stages of manufacture is used by the producers g iggf gfi jgg gfiggg and Hans Schlapfer, 5 as a check that the production steps proceed as desired.

Basel, Switzerland, and Christopher Johannes T inanufaumiing control difficult or immis- Tschamel. Warwick RL assignors to Geigy sible if the admixture of optical brlghtener leads to d1schemicalcorporafioil, Anisley a comma. coloration of the entire product during its manufacture.

tion of N Y k In Swiss Patent No. 321,109, optical brighteners are Filed May 12, 1967, Ser. No. 638,065 described which, because of good affinity to cellulose Claims priority, application Switzerland, May 13, 1966, fibers in a wide temperature range, are particularly suitv 19 55 2} Cu 9/44 able for use in washing liquors. An excellent, typical rep- U S 23/10 (309d r d 8 Claim resentative of thls group is the disodlum salt of 4,4'-bis- I I o x 8 [2" phenylamino 4 (N methyl l3 hydroxyethylamino) s triazinyl (6) amino] stilbene 2,2-

ABSTRACT OF THE DISCLQSURE gisulfonic acid. This group of valuable optical brighteners or washing agents, when used 111 a high concentration, incorporation in Solid detergents, the them'lostehle exhibits the disadvantageous discoloration of the washa-efyetal form of the Optical hrtghtehef, the dlsedlum ing powder mentioned above to a particularly marked Salt 0f his p y e y -fiydegree. For instance, if these products are incorporated dfeXY ethylamine) S y mm St in amounts of 3 kg. and more, in the usual way, into bene-2,2-disulfonic acid having an X-ray diffraction dia- 1000 kg, f washing powder, then these washing agents gram as shown in the accompanying Chewing, is Produced have an undesirable yellowish to yellow color which bey converting thermally instable terms of the abovecomes even deeper on storing when exposed to humidity named optical brightener to thermostable sodium salts 25 i h i y heating the thermally instable forms With a Water" It is known from th French Patent No. 1,361,065 that soluble, colorless sodium salt electrolyte in certain critical the ilk l salts f 4 4' b g" 4" h i amounts at a temperature 0f from about to triazinyl-(6)-amino]-stilbene-2,2-disulfonic acid, which can also be used as optical brighteners in washing agents,

can be converted into a more stable crystal form by heat- BACKGROUND OF THE INVENTION ing under pressure in the presence of alkaline substances. Field of the invention It would be obvious, therefore, to apply this process to the optical brighteners mentioned according to Sw1ss Patent No. 321,109 in order to attain in this way a more Zlnyt Stllhene optlcal bnghteher and t PTOFeSS stable modification which no longer discolors washing meklng the Same- More Partlcularly thls mvemlon P t agents. Rearrangement tests with such optical brighteners, tame to a thermostabte form of a particularly with the disodium salt of 4,4-bis-[2"-phenyl- (phenylamino-s-triazinylamino)-st1lbene, to a novel procamino (N methyl [B hydroxyethylamino This invention relates to a thermostable 4,4-bis-triaess for mtiking this X form @9 to detergents, soaps triaZinyl-(6")-amino]stilbene-2,2'-disulfonic acid, made and the hke eemposltlehe eohtelhlhg Sald hovel Crystal 40 under conditions completely analogous to those given in formthe French patent, however, yielded more or less strongly Descnptlon of Pnor art yellow colored products which did not produce the de- Th use of N,N bi -t i i l d i i of 4 4' di sired improvements on incorporation into the usual comaminostilbene-2,2'-disulfonic acid for the brightening of mereial heavy Washing agehte- In additlon, the French cellulose and polyamide substrates has been kiown for a 5 Patent 3 19 teaches that the pfetefred e considerable time and has been greatly extended for the 510R temperature e above and that lhorganle Salts optical brightening of textile material. This optical bright- Prevent the fofmatleh of the new K y form and thus ening is performed today not only by the textile producer are to removed before the Operatlenor finisher but, to an increasing extent, also by the housewife who washes her laundry with washing agents which DETAILED DISCLOSURE contain optical brighteners. in order to increase the In view of the above, it has surprisingly been found brightening effect, the suitable optical brighteners are that a crystal form which is thermostable in the aboveincorporated into the Washing agents during their producdescribed uses is obtained when an instable form such as tion. The goal of producing washing agents which imis obtained under normal production conditions, of

part to laundry (wash load) a whiter and whiter aspect Formula I has made it necessary for the producers of such washing wherein X represents two monovalent cations or one agent to constantly increase the amounts of brightener in divalent cation,

their Products' H relatively h Contents, in an aqueous electrolyte solution of sodium salts of in- 2 to 5 of bnghtenet' P ton of Washmg agent Whlch organic or organic acids, the concentration of said sodium has lately been used y y Producers, Causes Often a salts in said electrolyte solution being of sufficient amount distinct discoloration of the washing powder. This unto prevent the dissolution of the salt of Formula I, is

heated in a batch or continuous operation to temperatures between about 100 C. and about 200 C., optionally in the presence of alkaline substances, and, on completion of the conversion, the stable disodium salt, which is characterized by a definite crystal lattice, of Formula II r H CHzCHa-N is isolated. The thermostable crystal form so obtained is termed the a-form or lit-modification hereinbelow. In this process, the conversion proceeds very well even at relatively low temperatures of less than 140 C.; the process is substantially independent of the salt content of the starting material. Preferably the pH of the reaction mixture is 7 or higher.

The above-mentioned instable forms of a salt of the anionic optical brightener of Formula I are forms which are (1) either crystals which are not thermostable or (2) are insufiiciently crystalline to begin with; i.e. the crystallites or grains of such forms do not show any distinct, but at best diffuse, diffraction lines in their X-ray diffraction patterns, which latter can be obtained by the well-known powder technique using a Geiger counter or Proportional counter or the like instrument to record the intensity of the diffracted rays.

The X-ray patterns shown in the accompanying FIG- URE I were obtained by us by the well-known powder technique described, for instance, by Klug and Alexander in X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials, published by John Wiley and Sons, New York, N.Y. (1954) especially p. 235 et seq., using a Proportional counter-equipped goniometer made by N. V. Philips Gloeilampen-fabrieken, Eindhoven, Netherlands.

Here and in the following, the new a-crystal form of the stilbene derivative according to the invention as defined above is termed thermostable because it is thermostable up to at least 150 C., and, during and after incorporation into a moist washing agent containing sodium ions it is not converted into a yellow-colored form. We have found that of a dozen different crystal forms of the disodium salt of 4,4'-bis-[2"-phenylamino-4"-(N-methylfl-hydroxyethlyamino -s-triazinyl (6" -amino] -stilbene- 2,2'-disulfonie acid prepared by us, only the above u-form possesses this thermostability.

The crystalline a-form of the compound of Formula II has the form of needles, prisms or platelets and is characterized by an X-ray diffraction diagram having the following characteristic lines: a very strong line at 23.1 A., three strong lines at 5.46 A., 4.65 A. and 3.82 A., as well as four fairly strong lines at 10.2 A., 7.74 A., 6.90 A. and 3.09 A., as shown in the accompanying diagram.

The compound of Formula I used as starting material can 'be produced by known methods such as those described in Swiss Patent No. 321,109. For example, first one mol of 4,4'-diaminostilbene-2,2'-disulfonic acid and 2 mols of cyanuric chloride are reacted at -10 to +10 C., the intermediate product formed is then reacted at 0-30 C. with 2 mols of aniline, and finally, the remaining two chlorine atoms in the 4,4'-bis-[2"-phenylamino- 4"-chloro-s-triazinyl-(6")-amino]-stilbene 2,2 disulfonic acid so formed are exchanged for N-methyl-ethanol-amine radicals by heating the reaction mixture at 50-90 C. with excess amine. The reaction product is then generally isolated as a dialkali salt, preferably the SO Nu disodium salt. Produced under the usual conditions, depending on the method of isolation such as salting out with different salts or bases such as NaCl, Na CO NaOH, NH CI, precipitation with an acid and conversion of the inner salt obtained into another salt by treatment with a base, and also depending on the degree of drying,

these products have different crystal structures which, however, are not thermostable, i.e. on heating to a higher temperature, e.g. to above -100 C., they lose built-in water or solvent molecules and change into a more or less strongly yellow colored powder the texture of which as determined in the Philips Proportional counter goniometer may even have partly X-ray amorphous character.

Preferably the sodium or the inorganic or an organic ammonium cation is used as cation in Formula 1. Such ammonium cation is preferably of the formula Br, R

wherein each of R R and R is hydrogen, lower alkyl, hydroxy-lower alkyl,

or two of these Rs taken together form a polymethylene chain of from 4 to 6 CH -members one of which may be replaced by an oxygen atom. When cation therein represents a divalent cation such as magnesium or calcium, use of a sequestering agent in the mixture is mandatory.

The electrolytes used in the process of the invention must be water-soluble, colorless, and their anion must be heat-stable up to 200 C. in the reaction mixture and under the reaction conditions described above.

Mainly the halides such as chloride, bromide or iodide, and the salts of lower aliphatic, especially saturated unsubstituted or hydroxyl-substituted hydrocarbon carboxylic acids, but preferably lower fatty acids such as lower alkanoates, e.g. the formiate and acetate are used as sodium salts of inorganic and organic acids, with the help of which the conversion into the crystal modification is performed.

Preferably, these electrolytes are used as at least 2.5 N solutions; the upper concentration limit is their saturation. The concentration of sodium salt dissolved in the electrolyte in the reaction mixture should be sufficient to prevent the salt of Formula I from dissolving in the mixture, and should preferably be so great that there are at least 2 gram-ions of sodium to 1 mol of stilbene compound to be converted, i.e., that the conversion takes place at a pH which is at least about 7. In any event, the solubility rate of the electrolyte in the reaction mixture must be high enough so that sufficient amount thereof dissolves in the mixture to prevent the comopund of Formula I from dissolving therein. So that the reaction mixture can still be stirred well, it is advantageous to use at least 2 parts by volume of electrolyte solution to 1 part of stilbene compound.

The preferred reaction temperature lies between and C., and the reaction time can vary from a few minutes up to several hours.

The stilbene compound used as starting compound can optionally be used in the form of the free sulfonic acid or of its inner salt with the addition of bases in an amount sufficient for the desired salt formation.

In converting the compound of Formula I into the thermostable modification by means of the electrolyte solutions mentioned, advantageously an alkaline substance is added to the mixture. This addition of base is mainly indicated when an ammonium salt is used as starting material and it is necessary when the free acid is used so that the reaction takes place in a medium the pH of which is preferably at least about 7. At higher pH, the reaction time depends on the temperature applied and may range from 30 minutes to 24 hours, but should be interrupted as soon as the conversion of the brightener to the thermostable modification is complete as can be readily determined by control samples, and before any substantial saponification thereof has taken place. In addition, the base added protects the apparatus from corrosion. Also, other substances such as chelating agents or organic, hydrophilic solvents such as alcohols having 1-4 C atoms, lower alkyl ethers of glycols, or lower ketones can be added.

Alkaline additives can be both inorganic as well as organic compounds, e.g., alkali hydroxides such as NaOH or KOH; alkali cyanidcs such as sodium or potassium cyanide; alkali carbonates such as sodium or potassium carbonate; alkali phosphates; ammonia; organi bases such as mono-, diand tri-ethanolamine, mono-, diand tri-isopropanolamine, methylamine, diethylamine, tripropylamine, N-methyldiethanolamine, pyrrolidine, piperidine and morpholine, as well as their N-alkyl derivatives.

Examples of chelating agents are the alkali metal salts of nitrilotriacetic acid and of ethylenediamine N,N,N',N'- tetra-acetic acid.

Advantageously stainless steel apparatus constructed for an excess pressure of 1-6 atm. is used for the conversions. If the reaction mixture is brought to the desired reaction temperature in a relatively short time of 5-30 minutes, then melts are formed which later solidify in crystalline form and yield a coarse crystalline material having a high bulk density. These products have extremely low water solubility and have the most favorable behaviour with regard to discoloration of washing powders. If the suspensions of optical brighteners to be converted are slowly heated, i.e., for 3-6 hours, then a relatively fine, white suspension is formed. These products also are not thixotropic and can easily be filtered ofr and washed.

The conversion product isolated, e.g., by filtration, is advantageously washed, e.g., with a 5-15% solution of sodium chloride or the sodium salt used for the reaction. The main purpose of washing with sodium chloride or with another electrolyte containing sodium ions is to reduce the amount of electrolyte in the filter cake. Care should be taken, however, not to partially dissolve out the stilbene compound as this would again cause a yellow discoloration of the product because stilbene derivative dissolved in the washing liquor separates into a yellow modification on drying.

The new tit-crystal modification of the compounds of Formula II is distinguished by good stability to heat. Thus, for example, the tat-modification obtained according to the present process of the disodium salt of 4,4'-bis-[2"- phenylamino-4-(N-methyl-B-hydroxyethylamino) s-triazinyl-(6")-amino]-stilbene-2,2'-disulf0nic acid containing 1 mol of crystal water, which is particularly effective as a cellulose brightener, is stable up to towards 200 C. The new crystal form can best be characterized by an X-ray diagram. The method for taking this, described in the following Example 1, is suitable.

There are mainly two reasons why it could not have been foreseen that the process according to the invention would lead to a stable crystal modification. From the state of the art as mentioned, it was to have been expected that inorganic salts such as sodium chloride would prevent the production of a stable crystal form. The present invention has shown, however, that in this case, electrolytes are actually necessary for the crystal conversion. The French patent No. 1,361,065 also teaches that the conversion is advantageously performed at temperatures of over 145 C. It was, therefore, to have been expected that the production of stable crystals of products of Formula I would also be facilitated at temperatures of over 145 C. That the conversion can well be made at substantially lower temperatures is surprising. Working at lower temperatures means that no costly pressure apparatus is necessary as, at the reaction temperatures of -135 C. which are suitable in practice, the excess pressure always remains below 2 atm.

Solid detergents, including soaps and the like compositions to which the thermostable optical brightener according to the invention can be added at any step of their production are, more particularly, anionic detergents such as alkali metal salts of alkyl-aryl-sulfonates, especially alkyl-benzene and alkyl-naphthalene sulfonates, alkali metal salts of sulfates of higher fatty alcohol, or alkali metal salts of higher fatty acids, in which the cation portion consists preponderantly of sodium ions.

The following examples illustrate the invention without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 40 g. of the disodium salt of 4,4'-bis-[2"-phenylamino- 4"-(N-methyl B hydroxyethylamino)-s-triazinyl-(6")- amino]-stilbene-2,2'-disulphonic acid, produced according to Example 1 of Swiss Patent No. 321,109, are stirred into a homogeneous slurry in 200 ml. of 20% aqueous sodium chloride solution. 5 g. of sodium carbonate are added and the whole is poured into a 300 ml. stainless steel rotation autoclave. The pressure vessel, while continuously rotating, is slowly heated over a free gas flame until the inner temperature, measured with a central thermometer tube, has risen to The heating time is 4 hours. The mixture is then kept for 4 hours at 12S130. The yellow modification of the stilbene compound used is changed into the practically colourless suspension of the new a-crystal modification. After cooling, the product is filtered off, washed with 10% sodium chloride solution and dried in vacuo at 80. In this way, a white powder is obtained which fiuoresces blue in UV light.

If 4 g. of the brightener obtained in this way are mixed with an aqueous slurry of 1000 g. of a commercial heavy Washing agent and then dried, a clearly brightened washing powder is obtained whilst a washing combination produced in an analogous way with the previously known brightener modification has a yellowishtinge.

To characterise the new crystal modification, an X-ray diagramme was taken both of the starting material and the new wcrystal modification. This can be seen from the attached drawing and was obtained by the method described below.

The starting material and the new crystal modification differ from each other by the interplanar spacings (dvalues).

To determine these interplanar spacings, X-ray diffraction patterns were produced by the technique mentioned further above with the Philips Proportional counter goniometer. The instrument actually records the intensity of the diffracted ray on the vertical axis versus the angle of diffraction on the horizontal axis with CuK, radiation, and then this angle is converted to interplanar spacings expressed in Angstrom units. The values given are accurate to within 2 percent and in most cases, particularly with d-values of less than 10 A., variation is less than 1%. Therefore, this variance should be taken into account when interpreting the specification and the appended claims.

The starting material is characterized by a very strong line at d=18.0 A. and three fairly strong lines at 9.9 A., 6.10 A. and 3.42 A. In addition there are a few weaker lines.

In a contrast, the new a-crystal modification is characterized by a very strong line at d:23.1 A., three strong lines at 5.46 A., 4.65 A. and 3.82 A. as well as four fairly strong lines at 10.2 A., 7.74 A., 6.90 A. and 3.09

A. The weaker lines and lines common to both crystal modifications have been left out.

EXAMPLE 2 In a 3500 ml. stainless steel autoclave fitted with a stirrer, 130 g. of disodium salt of 4,4-bis-[2"-pheny1- amino-4"-(N-methyl B hydroxyethylamino)-s-triazinyl- (6")-amino]-stilbene-2,2-disulphonic acid, produced according to Example 1 of Swiss Patent No. 321,109, are suspended in 1500 ml. of aqueous sodium chloride solution. 4 g. of triethanolamine are added and the whole is heated to 120 within 4 hours. The mixture is then stirred for 6 hours at 120-125". After cooling, the white suspension is filtered under suction, the residue is washed with 10% sodium chloride solution and the compound is dried at 80 in vacuo. The white product containing sodium chloride obtained according to the process has the same crystal structure as the product obtained according to Example 1.

A sample thereof washed with water is dried for 14 hours under high vacuum at 135 and analysed. The analysis showed C H N O S IH O calculated: 49.7% C, 4.4% H, 18.3% N, 7.0% S. Found: 49.7% C, 4.5% H, 18.1% N, 6.8% S.

The 1 mol of crystal water is so strongly bound that also drying at 160 does not yield a product containing less water. This behaviour shows the stable incorporation of the water molecule into the crystal lattice.

EXAMPLE 3 17 g. of the stilbene compound used as starting material in Example 1 in 200 ml. of sodium chloride solution are heated in an autoclave for 6 hours at 130- 137". A pale grey hard mass is obtained which is crushed, washed with 2.5% sodium chloride solution and dried at 80 in vacuo. The product obtained forms a pale beige powder and, as is shown by the X-ray diagramme, consists mainly of the tat-modification characterised in Example 1.

EXAMPLE 4 160 g. of the disodium salt of 4,4-bis-[2-phenylamino 4" (N methyl 3 hydroxyethylamino) strizinyl (6") amino] stilbene 2,2 disulphonic acid produced according to Example 1 or Swiss Patent No. 321,109, are slurried in 1500 ml. of 25% sodium chloride solution. After adding 5 g. of triethanolamine,

5 g. of sodium carbonate and 5 g. of the sodium salt of ethylenediamine N,N,N',N tetra acetic acid, the whole is heated for 10 hours while stirring in a stainless steel autoclave fitted with a stirrer at 130-134. After cooling, the crystal product formed is filtered off, washed with 10% sodium chloride solution and dried in vacuo at A white crystal powder containing sodium chloride is obtained, the crystal structure of which corresponds to the product of the process according to Example 1.

EXAMPLE 5 22 g. of bis-diethanolamine salt of 4,4'-bis-[2"-phenylamino 4" (N methyl 18 hydroxyethylamino)- s triazinyl (6") amino] stilbene 2,2 disulphonic acid, 135 ml. of water, g. of crystallised sodium acetate, 0.8 g. of sodium salt of ethylenediamine- N,N,N',N-tetra-acetic acid and 5 g. of sodium carbonate are heated in a rotation autoclave to 130 within 40 minutes and then for 4 hours at 125130. After cooling, the almost colourless crystal mass is separated from the mother liquor, crusted in a mortar, washed with water and dried in vacuo at 80. The product obtained contains 1 mol of crystal water and possesses the u-modification. Analysis showed: C H N O S Na -H O calculated: 49.7% C; 4.4% H; 18.3% N; 7.0% S. Found: 49.6% C; 4.6% H; 18.0% N; 6.7% S.

The following salts are converted into the desired tat-modification of the disodium salt in an analogous Way: di-ammonium salt, di-monoethanolamine salt, di-potassium salt, di-triethanolamine salt, di-methylamine salt, bis-di-isopropanolamine salt, bis-dimethylamine salt, dimorpholine salt, di-triethylamine salt, di-N-methylmorpholine salt, di-pyrrolidine salt, di-piperidine salt, di-N- methyl-ethanolamine salt and di-N-methyl-dietanolamine salt. The salts used as starting materials can be produced as follows:

250 g. of the disodium salt are dissolved at 90 in 3000 ml. of water and, at 90-95, 40 g. of acetic acid are added within 15 minutes while stirring. A thick slurry is obtained which, to facilitate filtration, is stirred for 1 hour at 90. The mixture is then cooled within 1 hour to 45 the yellow precipitate is filtered off under suction and washed with 500 ml. of water. To convert into the corresponding salts, the inner salt of the disulphonic acid obtained in this way is stirred in water and the pH is adjusted at 80-90 to 8.5 with excess base. The salt is then isolated by evaporation in vacuo or crystallisation.

Further examples for the production of the stable onmodification of the optical brightener of the formula SO Na are summarised in the following table. In Examples 6- 38 and 44-50 g. of the disodium salt and in Ex- 60 amples 39-43 100 g. of the bis-diethanolamine salt are used as starting material. Otherwise the procedure is similar to that of Example 1.

Temper- Reaction Ex. ature, time in No. Electrolyte Alkalme substance Additives degrees hours 6 1,250 ml. NaCl 10%. 3 g. tricthanolamine 120-125 14 7 670 ml. NaCl 15% 1.7 g. triethanolamine -120 8 1,250 ml. NaCl 15%. 2 g. triethanolamine -125 6 9 1,250 ml. NaCl 15%. 4 g. triethanolamine 155-160 1 10 1,2501'1'11. NaCl 20%. -145 4 11"... 1,250 ml. NaCl 20%. 3 g. triethanolamine -160 1 12... 1,250 ml. NaCl 25%. 6 g. triethanolamine 115-120 0 13 1,250 ml. NaCl 25% 3 g. triethauolamine 120-125 6 14- 500 ml. NaC125% 12.5 g. Na COa $6 15. 1,150 ml. NaOAc 24% 35 g. NBQCO: 1.3 g. ED'IA--. 120-125 4 l6 900 ml. NaOAc 24% 10 g. Na CO 1.3 g. EDTA.-- 125-130 4 17... 900 ml. NaOAc 24% 10 g. NazC'o 1.3 g. EDTA. 125-130 8 18 1,000 ml. NaOAc 24%. 5 g. triethanolamine 120-134 14 Ex. No. Electrolyte 1,000 ml. NaOAc 24% 21 1,130 m 0 m1. NaOAc 30% 44 750 ml. NaCl 600 ml. NagSO 20% 45-.- 750 ml. NaCl 25%, 500 ml. NarSO 20%- 500 m1. NaCl 20%, 750 ml. NaOAc 22% 1,000 ml. NaC125% 250 ml. NazSO 20%, 300 ml. NaOAe 24%, 450 ml 600 g. NaN

48. 49 02, 1,000 ml. water 50 2,700 g. NaClOg, 5,000 ml. water 50 g. Natooa II In the above examples, EDTA means the tetra-sodium salt of ethylenediamine-N,N,N,N-tetraacetic acid and Ac means the acetyl radical.

EXAMPLE 51 40 g. of the disodium salt of 4,4'-bis-[2"-phenylamino- 4" (N methyl 3 hydroxyethylamino) s triazinyl- (6)-amino]-stilbene-2,2-disulphonic acid produced according to Example 1 of Swiss Patent No. 321,109, are suspended in 400 ml. of a 2.5 N solution of the sodium salt of glycolic acid and, after the addition of 4 g. of sodium carbonate, the whole is heated for 6 hours at 130135. After cooling, the almost white suspension obtained is filtered, the residue is washed with 15% sodium chloride solution and dried in vacuo at 80. The crystal product obtained has the same stable crystal structure as the product obtained by the process of Example 1.

If in the above example, the 400 m1. of 2.5 N solution of sodium salt of glycolic acid are replaced by 400 ml. of 2.5 N solution of sodium salt of diglycolic acid, then the desired tat-modification is also obtained.

EXAMPLE 52 g. of the dipotassium salt of 4,4-bis-[2"-phenylamino-4"-(N-methyl B hydroxyethylamino) s triazinyl-(6)-amino]-stilbene-2,2'-disulphonic acid are stirred into a homogeneous slurry in 400 ml. of 15% aqueous sodium chloride solution and, after adding 3 g. of sodium carbonate, the whole is heated for 8 hours at 125-130 while rotating. After cooling, the white crystal slurry is filtered off, the residue is washed with 10% sodium chloride solution and dried at 80 in vacuo. In this way the disodium salt of the optical brightener used in the ocmodification characterised in Example 1 is obtained.

The dipotassium salt used as starting material is prodiiced as follows: 28.6 g. of the disodium salt are converted into the free acid by the method given in Example 5, this is dissolved in 500 ml. of water, with the addition of 7 g. of potassium hydroxide, at 90-100", the solution is clarified while hot and the yellowish filtrate is allowed to cool. The dipotassium salt crystallizes out in the form of fine yellow crystals.

EXAMPLE 53 0.35 g. of the optical brightener obtained according to Example 1 are stirred into 3.5 m1. of 1 N sodium hydroxide solution and then worked up into a homogeneous paste with 100 ml. of Water and 100 g. of a heavy duty detergent consisting of:

Alkaline substance 19- 1,000 ml. NaOAc 24% 10 g. diethauolamine 10 g. isopropanolamiue-. 10 g. morpholine 50 g. monoethanolamine.

20 ml. cone. ammonia g. triethanolamine. g. triethanolamine Reaction time in hours Temperature,

15.2 parts of sodium dodecylbenzene sulphonate,

3.8 parts of sodium lauryl sulphate,

25.6 parts of sodium tripolyphosphate,

7.6 parts of tetrasodium pyrophosphate,

4.8 parts of sodium silicate,

1.9 parts of magnesium silicate,

5.0 parts of sodium carbonate,

1.4 parts of carboxymethyl cellulose,

0.3 part of sodium salt of ethylenediamine tetra-acetic acid and 34.4 parts of sodium sulphate.

The mixture is then dried at crushed and finally pressed through a sieve.

The washing powder obtained has a substantially more white appearance in daylight than a comparative sample which has been brightened with the instable crystal modification of the same optical brightener.

The following detergent compositions were prepared in a similar manner to that of Example 46:

EXAMPLE 54 100 pounds of cocoanut oil are melted in a jacketed pan and, after settling, passed through a fine linen cloth or hair-sieve to remove any impurities. The oil is then run into the stirring kettle and when cooled to F., 54 pounds of caustic soda lye of 38 B. are run into it in a thin stream with constant stirring until the oil is completely saponified and, while the mass commences to thicken, 4 oz. (about 112 g.) of the thermostable optical brightener obtained according to Example 1, stirred into 1 liter of cold water are added gradually during the stirring. The mass is then cooled by stirring and finally brought into the frames, in which it is allowed to slowly congeal.

A fine, white, optically brightened soap is thus obtained.

EXAMPLE 55 A heavy duty detergent of similar advantageous properties as that of Example 53 is prepared in the manner described in that example, as follows:

5 liters of 1 N-sodium hydroxide solution into which 500 g. of the thermostable optical brightener of Example 1 have been stirred are worked up into a homogeneous part with liters of water and 100 kg. of a batch consisting of 20 parts of sodium dodecyl-benzene sulfonate 5 parts of sodium metasilicate 1 l 1 2 15 parts of sodium sulfate and otherwise the procedure given in Example 53 is fol- 0.8 part of carboxymethyl-cellulose and lowed, then a washing agent having a high degree of 9 parts of water. whiteness is also obtained.

We claim:

Drying, crushing and sieving of the mixture follows r 1. The thermostable crystal form of the optical brightas described in Example 53. ener of the formula CH3 CH3 sloaNa N N\ \C-NH@CH=CII@NHC N .Ino

SOaNa EXAMPLE 56 characterized by an X-ray diffraction pattern having the following characteristic lines corresponding to: a very A batch consisting of strong line at 23.1 A., three strong lines at 5.46 A., 4.65 A.

and 3.82 A. and four fairly strong lines at 10.2 A., 7.74 A., 51 parts of sodium n-dodecylbenzyl sulfonate (45% and active) 2. A process for the production of a thermostable crys- 24 Parts of Sodlum y ne sulfonate (40% active) 20 tal form of a bis-triazinylamiino-stilbene derivative, com- 10 parts of nonylphenoxy polyoxyethylene ethanol prising; 7 parts of lauroyl diethanolamlde and mixing a thermally unstable form of the compound 8 parts of water of the formula:

$H3 CH3 HOCHzCH2- SO5X I l-0112011 011 s mixed With 100 Parts of Water and 2 Parts Of 3 wherein X represents an alkali metal ion or an normal sodium hydroxide solution containing 0.2 part ammonium i f the f l of the thermostable optical brightener of Example 1, dispersed therein. The mixture was further treated as described in Ex- N ample 53 and an excellent detergent for use in household washing machines was obtained.

wherein each of R R and R represents hydrogen, EXAMPLE 57 lower alkyl, or hydroxy-lower alkyl, or R and R A b t h consisting f when taken together with the nitrogen atom to which they are linked represent pyrrolidino, piperidino or 25 parts of nonylphenol polythylene glycol ether (mole morpholino, g??? of nonylphenol to ahylene Oxlde about to with an aqueous solution of an electrolyte of the class consisting of a water-soluble, colorless sodium salt of a mineral acid and the water-soluble sodium salt of a lower aliphatic saturated unsubstituted or hydroxyl-substituted hydrocarbon monoor di-carbox- 25 parts of sodium tripolyphosphate, hydrated 5 part of disodium phosphate 25 parts of sodium sesquicarbonate and 25 parts of sodium chloride ylic acid, or mixtures thereof, are intimately mixed for six minutes on a ribbon mixer the concentration of the sodium salt in said aqueous with 0.5 part of the thermostable optical brightener of electroly t o being of at least a normality of Example 1. 2.5 and sufiicient to prevent the compound of For- A h d di h hi powder of t bl hit aspect is mula I from dissolving in said electrolyte solution, b i d the anion of said electrolyte being heat-stable in EXAMPLE 58 the reaction mixture under the reaction conditions defined below, heating said mixture to a temperature of from about to 200 C., thereby converting said instable If, in Example 53, the 100 g. of washing agent are replaced by a heavy duty detergent consisting of 7.8 parts of sodium lauryl sulfate, 0 form to the thermostable form of the compound of 11.0 parts of sodium dodecylbenzene sulfonate, the formula:

(3113 CH, nooHmm-N SOaNa r l-omomolr 11.0 parts of sodium tripolyphosphate, 70 and recovering the said thermostable form from 16.6 parts of tetrasodium pyrophosphate, the conversion reaction mixture.

4.6 parts of sodium silicate, 3. A process as described in claim 2, wherein said teml.4 parts of carboxymethyl cellulose, perature is in the range of about to C.

36.8 parts of sodium sulfate, and 4. A process as defined in claim 3, wherein said elec- 8.0 parts of sodium perborate (NaBO -4H O) 75 trolyte is a sodium halide.

13 5. A process as described in claim 3, wherein the reaction mixture is maintained during the conversion reaction at a pH of at least approximately 7 or higher. 6. A process as described in claim 2, wherein X in Formula I represents sodium.

7. A process as described in claim 5, wherein said electrolyte is sodium chloride.

8. A process as described in claim 2, wherein the heating of said mixture is carried out at an excess pressure of about 1 to 6 atmospheres above ambient pressure.

1 4 References Cited UNITED STATES PATENTS 2,762,801 9/1956 Hausermann 260240 XR FOREIGN PATENTS 1,361,065 4/ 1964 France.

JOHN D. RANDOLPH, Primary Examiner U.S. Cl. X.R. 1l7-33.5; 2S2ll7, 137, 301.2 

